CA1325312C

CA1325312C - Method for enhancing the polymerization activity of crude cycloolefin monomers for bulk polymerization

Info

Publication number: CA1325312C
Application number: CA000592682A
Authority: CA
Inventors: James T. Ware; Robert J. Minchak
Original assignee: BF Goodrich Corp
Current assignee: Goodrich Corp
Priority date: 1988-04-08
Filing date: 1989-03-03
Publication date: 1993-12-14
Anticipated expiration: 2010-12-14
Also published as: BR8901054A; EP0336105A2; US4843185A; MX165301B; EP0336105A3; JPH0284428A

Abstract

TITLE OF THE INVENTION

METHOD FOR ENHANCING THE POLYMERIZATION ACTIVITY OF
CRUDE CYCLOOLEFIN MONOMERS FOR BULK POLYMERIZATION

ABSTRACT
A process for enhancing the polymerization activity of mixtures of one or more cycloolefin monomers is provided by treatment with heat. This process can be easily incorporated into ring-opening, bulk polymerization methods and methods which form high molecular weight monomers. Enhancing the polymerization activity of crude mixtures of cycloolefin monomers by this process permits polymers having higher glass transition temperatures and higher heat distortion temperatures to be produced with greater economy.

Description

132~312 FIELD OF THE INVENTION: -Thi~ invention is directed to improving the qu~lity o~ crude cycloolefin monomers which contain a norbornene group. More particularly, this invention is directed to a method for enh~ncing the polymerization activity of crude cycloolefin monomers for polymerization in bulk, such a~ by reaction in~ection molding ( RIr,l ) techniques , to provide copolymers with high hest . -: -~stability.

BACRGROUND OF TH~ I~VENTION:
~ . -Cycloolefin monomers (cycloolefins) which contain a norbornene group are known to polymerize by ring-opening polymerization and addition polymerization. Polymers obtained by ring-opening polymerization of cycloolefins that contain a norbornene group are well known. For example, U. S. patent numbers 4 ,13B, 249; 4 ,178, 424; 4 ,136, 247 and 4 ,136, 248, a~signed to the same assignee of the present invention, describe such - --polymers, -~ ~
. . , :
Ring-opening polymerization of cycloolefins yields unsaturated linear polymers which are of particular interest in ; . -:
that they are known to be reactive (sulfur-vulcanizable) and A ~ :

they are known to exhibit attractive property profilea with good heat distortion temperatures for many polymer applications, such as, for example, a~ automotive part~, psrticularly body panels, bumpers, facia, etc. Many of these polymer properties, such as heat dictortion temperature, are dependent on a high degree of conversion of the cyclooleffn monomer into polymer. Thi~ is particularly true in bulk polymerization processes where any unreacted monomer will remain dispersed in the finished article, providing an undesired plasticizing effect and/or this unreacted monomer may leach from the molded part, rending the ~inished article less useful. It is known a substanffally pure feedstoclc of cycloolefin monomers will help provide a high degree of conversion in bulk polymerizaffon processes, and may often be necessflry to provide useful finished artlcles. A cycloolefin monomer feedstock of over 99% purity is often desired in RIM
techniquec, which is a common example of a bulk polymerization process.
Dicyclopentadiene is a common cycloolefin monomer used to prepare ring-opening polymerized polymers. Recent U, S .
Patents directed to dicyclopentadiene polymers include U . S .
Patent Nos. 3,778,420; 3,781,257; 3,790,545; 3,853,830 and 4,002,815. Dicyclopentadiene monomers are by-products in ethylene production and are comslercially available in different grades of purity. The commercial crude grades of 97% to 98%
dicyclopentadlene do not yield the rapid reactions nor high conversion desired for ring-opening polymerization. The more costly 99% pure dicyclopentadiene shows the necessary quality for both high activity and high conversion. It is desirable to develop a s{mple means to enhance the polymerization activity of the less pure dicyclopentadiene grades to provide the desired activity and conversion.
Purification of other cycloolefin monomers for use in ring-opening bulk polymerizations is also desired. For example, norbornene (bicyclo(2.a.1)hept-2-ene), substituted norbornenes.
tetracyclododecene, substituted tetracyclodocenes, and higher homologs OI these with cyclopentadiene, ~re known to be ~ -.. . . . . . . . ... . ... . .

-3~ ~32~312 produced by the Diels-Alder re~ctlon of cyclopentadiene ~nd selected olefins. Often a m~cture of products i8 obt~ined from these reactions, requ{ring purification. A less costly purification process would be a grest advantage in utilizing the cycloolefin monomers synthesized from dicyclopentadiene.
Heat treatment of a polymerization grade cycloolefin feedstock is known to yield a product containing cycloolef ins with increased molecular weight. The heat tre~tment does not affect the reaction rate or the degree of convers ion of the monomers. The monomers are still of polymerization grade after heat treatment.
It has now been discovered that the heat-soalcing procedure (or heat treatment) of commercisl crude grade 97-98%
pure dicyclopentadiene enhsnces its polymerlzation activity by reducing the quantity of polymerizatlon retarding impurities.
This treated crude dicyclopentadiene provides the rapid polymerization rate~ and high monomer conver~ation desired from the high quality, commercial polymerization grade, 99% pure -dicyclopentadiene.

SUMMARY OF THE INVENTION:

This invention providss a method for enhancing the polymerization activity of crude grade mixtures of cycloolefin monomers to provide a feedstock suitable for bulk polymerization.
Thi~ is accomplished by heating a crude mixture of one or more cycloolefin monomers containing polymerization retarding -impurities wherein the cycloolefin monomers have at least one norbornene group. The cycloolefin monomer~ are prefersbly bicyclooleflns and tricycloolefins such as dicyclopen~adiene.
This crude grade m~cture of one or more cycloolefin monomers is heated to a temperature sufflciently high and for a period ~ufficiently long to dissociate a portion of the cycloolefin monomers, giving cyclopentadiene therein, and to react the cyclopentadiene product wit}~ polymerization retarding impurities -. ..-' -~.

:

in the crude mixture, such as linear olefinic impurities and oxygen containing impurities. The crude mixture of cycloolefin monomer~ is m~intained substantially free of a complete polymerization catalyst/co-cat~lyst system during heating to prevent polymerization.
Another embodiment of this invention is a ring-opening bulk polylDerization process wherein a crude mixture of one or more cycloolefin monomers, comprising at least 25% by weight dicyclopentadiene based on the weight of said crude mixture, is heated or heat-soalted to increase polymerization activity and is then bulk polymerized to obtain ring-opened polymerized polymers having high glass transition temperature values.
Also provided by this invention are method~ for producing polymers from a crude mixture of one or more cycloolefin monomers by ring-opening bulk polymerlzation wherein the cycloolefin monomers are heated to provide both ( 1 ? an improvement in polymerization activity (or monomer quality) and (2) an increase in the molecular weight of the cycloolefin monomers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention herein is bssed on the discovery that crude mixtures of cycloolefin monomers such as dicyclopentadiene, which normdly contain polymerization retarders such a8 linear olefins and diolefins and often oxygen containing products, can be improved in polymerization quality when heated to cause dissociation of the cycloolefin monomers giving cyclopentsdiene.
The dissociat~on of the cycloolefin monomers is advantageous to the polymerization quality of such a crude cycloolefin mixture in that cyclopentadiene reacts or renders harmless the polymerization retarders therein, such as the linear olefins and diolefins. It is preferred that dicyclopentadiene be present within the cycloolefin monomers utilized.
The cyclopentadiene may also react wiSh the norbornene group of other cycloolefin monomers within the mixture, thereby . . .
, ," , _5_ ~3~3~2 forming cycloolefin monomers with increased molecular weight.
The quantity of cyclopentsdiene within the volume of cycloolefin monomers remains low because of their reactivity in forming Diels-Alder products with olefinics. This small quantity of cyclopentadiene does not affect the degree of conversion of the cycloolefln monomers in ring-opening polymerization procedures in that cyclopentadiene also participates in the bulk polymerization .
The one or more cycloolefin monomers which can be treated by the process described herein to provide enhanced polymerization activity are characterized by the presence o~ at least one norbornene group represented by Formula I below, which can be substituted or unsubstituted.
.: ..

I ;
' ' ' ~ '' ~

Pursuant to this definition, suitable cycloolef~n monomers include substltuted norbornenes and unsubstituted norbornene, dicyclopentadlene, dihydrodicyclopentadiene, cyclopentadiene trimers, cyclopentadiene tetramers, cyclopentadiene pentamers, tetracyclododecene, substituted tetracyclododecenes and hexacycloheptadecene. The more common cycloolefin monomers con~orm to Formulss II, III and IV below~
. -,., ; .
I~

[~ Rl Il /~ R

wherein R and Rl ar~ independently selected from hydrogen, -hdogen, C1-C12 alkyl groups, C2-C12 alkylene groups~ C6~C12 , ~-cyclodXyl groups, C6-C12 cycloslkylene groups and C6-C12 aryl ~ . .
~ : .

.

-6 1~2~312 groups or R and R1 together form 88turated or unsaturated cyclic groups of from 4 to 12 carbon atoms with the two ring carbon atoms connected thereto, ssid ring carbon atom~ forming part of and contributing to the 4 to 12 carbon atoms in the cyclic group. Examples of common cycloole~n monomers conforming to Formul~s II and III include 2-norbornene, 5-methyl-2 -norbornene, 5, 6-dimethyl-2-norbornene, 5-ethyl-2 -norbornene, 5-ethylidenyl-2-norbornene, 5-butyl-2 -norbornene, 5 -hexyl-2 -norbornene, 5 -octyl- " -norbornene, 5 -dodecyl- 2 -norbornene, 5-isobutyl-2-norbornene, 5 -oct~decyl- 2-norbornene, 5-isopropyl-2 -norbornene, 5-phenyl-2-norbornene, 5-p-toluyl-2-norbornene, S-~-naphthyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5, 5-dimethyl-2-norbornene, dicyclopentsdiene (or cyclopentadiene dimer), dihydrodicyclopentadiene (or cyclopentene-cyclopentadiene co-dimer), methyl - cyclopentsdiene dimer, ethyl - cyclopentadiene dimer, tetracyclododecene 9-methyltetracyclo 16, 2 ,1,13 ~ B, o2 ~ 7 ] dodecene-4, (or 9-methyltetracyclododecene-4 or :~
methyltetracyclododecene) 9-ethyltetracyclo[6,2,1,13'6,02'7]dodecene-4, (or 9-ethyltetracyclodedecene-4 or ethyl-tetracyclododecene) 9-propyltetracyclo[6,2,1,13'6,02'7]dodecene-4, 9-~exyltetracyclo[ 6, 2 ,1,13 ~ 6, o2 ~ 7 ] dodecene-4, .
-132~312 9-decyltetracyclo[ 6, 2 ,1,13 ~ 6, o2 ~ 71 dodecene-4, 9 ,10-dimethyltetracyclo~ 6, 2 ,1,13 ~ 6, o2 ~ 7 ] dodecene-~, 9-methyl,10-ethyltetracyclo[6.2,1,13'6,02'7]dodecene-4, 9-cyclohexyltetracyclo[6,2,1,13'6,02'7]dodecene-4, 9-chlorotetracyclol6,2,1,13'6,02'7]dodecene-4, 9-bromotetracyclo ~ 6, 2 ,1,13 ~ 6, o2 ~ 7 ] dodecene-4, cyclopentadiene trimer, methyl-cyclopentadiene trimer, ethyl-cyclopentadiene trimer, dihydro-cyclopentadiene trimer, and the like.
The most common cycloolefin monomer is dicyclopentadiene.
It is commercislly available at variou~ grades of purity.
Dicyclopent~diene is also the preferred cycloolefin monomer because it cracks to cyclopentadiene at lower temperatures than the other cycloolefin monomers of ~ormulas II and III. The crude cycloolefin monomer mixture generally contains at least 10%
by weight, preferably at least 25% by weight, dicyclopentadiene, to provide cyclopentadiene dissociation products. ~- -;
The most common crude grade~ of dicyclopentadiene contain various polymerlzation retsrders such as linear olefins and diolefins ~rom the synthesis of the cycloolefin monomers. Olefin functionality is evidenced by the reactivity of the impurittes with the dicyclopentadiene reaction product. The proce~s of this t invention will readily improve the polymerizability ~f such mixtures: by reacting the olefinic impurities therein with the cyclopentadiene dissocistion product formed during craclcing.
The process of this invention i5 al30 capable of reducing the ~ ~ -quantity of reactive polymerization retarders from other source~
such as from the degradstion of the cycloolefin monomers or from contamination by unclean equipment or from intenffonal addition ~ ~ -of ~ such retarder~. Oxygen containing compound~, ~uch as - -i oxides and epoxides, may also be present in crude mixtures of cycloolefin monomers and they sre also polymerization retarders.
The identity and source of some polymerization retarders is ,.
dimcult to determine by conventional techniques because of the . '-' -; ' '`.: ' -8- 1~2~3~

small quantities present in the crude mixture. Gas chromatography in combination with mass spectro8copy may be helpful as an identification tool. In addition, mixtures of polym~rization retarders may be expected, making their indentification and their source more difficult to determine. The type of polymerization retarders in the cycloolefin mixture will vary due to many factors, such as, for example, the cycloolefin monomers within the crude mixture, the starting materials used in synthesizing these cycloolefin monomerQ, the conditions which generated the impurities, etc.
The process of thi3 invention will provide polymerization grade cyclooleffn monomer products from crude grade cycloole~n monomers having higher levels of polymerlzation retarder~ than commercial crude grade 97-989~ dicyclopentadiene. The process of this invention will handle quantities of polymerization retarders of over 5% by weight of the total cycloolefin monomers.
The process of this invention i9 ineffective in reducing the quantity of saturated impurities. However, these saturated impurities will not hinder the effectiveness of the process of the invention in reducing the linear olefinic impurities and other polymerizaffon retarders present in the crude mixture.
The level of polymerization retarders which can be handled is dependent on the quantity of dicyclopentadiene within the cycloolefin monomers treated. There must be sufficient dicyclopentadiene to crack to cyclopentadiene and react with ole~inic impuritie3 and tie up, eliminate or reduce the retarding effect of oxygen containing impurities so that polymerizaffon grade monomer results. The idenfffication of these polymerization retardants is complicated by (1) the small quanffties present, (2) the large variety of species present, such as the oxygen containing compound~, and (3) the presence of inert impurities. Therefore, the most convenient method for determining feedstock quality and uti}ity for use in the process of the invention is to sample the feedstock, apply the proces~ of this invention to the ~ample and analyze the polymerizat{on of the monomer feedstock sample.

-9- 132~312 As indicated above, the polymerization retarders reduce the degree of monomer conver8ion to polymer product. These polymeriz~tion retarders are generally present in crude cycloolefin mixtures in quantities less than 0 . 25 weight percent and as high as 1 to 10 weight percent. The quantity of these polymerization retarders generally reduces the degree of conversion of monomer to polymer by at least 1%. The polymerization retarders within the crude mixtures of cycloolefin monomers are preferably reduced or rendered inert to a level sufficiently low to permit at least about 90% conversion of the cycloolefin monomers to polymer snd to provide ~n increase in monomer conversion of at least 1% and up to 10% or more as determined by the difference in weigh~ of a polymerized sample before and after thermal gravimetric analysis on a DuPont 1090 thermal analyzer on heating a sample up to about 400C.
Obtaining a degree of con~rersion higher than 97% is more desirable and approaching 100% conversion of cycloolefin monomer is most preferred. The quanffty of dicyclopentadiene Qay decrease after heat treatment where a portion dissociates to react with any olefinic impurities.
After enhancing their polymerization activity by the process of this invention, the cycloolefln monomer3 are formulated into a feedstock. The bulk polymerization feedstock may contain consfftuents other than the cycloolefin monomers. Other cumponents of the polymerlzation feedstock may include the polymerization catalyst components and common additives. The components of the complete catalyst / co-catalyst system are generally separated into two or more streams of the heat-treated mixture of cycloolefin monomers. All components of the ~atalyst cannot be present within the treated mixture of cycloolefin monomers in that polymerization will commence. Either the catalyst or co-catalyst component may be present within a heat-treated mixture before use, but not both. Where desired, two separate heat-treated mixtures may be provided, one with catalyst and the other co-catalyst. Both heat-treated mixtures :

-lo. 1325312 are then combined to form the complete cataly~t/co-catalyst system and initiate polymerization.
For certain bulk polymerization procesaes, it may be mo~t convenient for the catalyst or co-catalyst to be present during heat trestment of the crude mixtures by the process of this invention. It is recognized however, that these compounds may be added to the crude mixtures after heat treatment and still provide bulk polymerization.
Examples of bulk polymerization catalysts ~nclude, the organoammonium molybdates and tungstates represented by the formulas below:

4 (2y-6x) x y V
and . . .
[ R34 ~JH ] ( 2y- 6x ) MxOy VI

wherein 0 represents oxygen; M represents either molybdenum or tungsten; x and y represent the number of tungsten/
molybdenum and oxygen atoms in the molecule based on a valance of +6 for molybdenum, +6 for tungsten and -2 for oxygen; and the P~ and R substituents can be the ssme or diffarent and are selected from hydrogen, alkyl and alkylene groups each containing from 1 to 20 carbon atoms and cycloaliphatic groups each containing ~rom 5 to 16 csrbon atoms. All of the R2 and R substltuents csnnot be hydrogen~ nor be small in number of carbon atoms in thst such a condition will render the molecule essentially insoluble in hydrocarbons and most organic solvents.
A more detailed description of these organoammonium molybdates and tungstates appears in U.S. Patent 4,426,502 assigned to the same assignee as the present invention.
Specific examples of suita~l organoammonium molybdates and tungstates include tridodecylammonium molybdates and tungstates, methyl tricaprylammonium molybdates~ and tungstates, tri~tridecyl)-A --11 13253~2 ammonium molybdates and tungstates and trioctylammonium molybdates and tungstate~.
The presence of these bulk polymerization catalysts or co-catalyst~ within the crude mixture of cycloolefin monomers does not inhibit the objectives of the present invention in providing purified cycloolefin monomers for polymerization in bulk. The quantity of catalyst or co-catalyst present is generally dictated by the needs of the subsequent bulk polymerization reaction and the resulting products desired.
Examples of co-catalysts used in bulk polymerizations are aryloxyalkylaluminum halides and alkoxyalkylsluminum halides of the formula (R40)a R5bAlXc, where R4 i8 an alkyl or phenyl group containing about 1 to 18 cerbon atoms, preferably 2 to 4;
R5 is an alkyl group contsining 1 to 18 carbon atoms, preferably 2 to 4; X is a halogen selected from chlorine, iodine, bromine and fluorine, preferably chlorine and iodine; "a" is the number of equiYalents of the alkoxy or aryloxy moiety and can vary from about 1/ 2 to about 2, preferably from about l to about 1 1/ 2;
"b" is the number of equivalents of the alkyl group and can vary from a minimum of about 1/ 4 to a maximum of about 2, preferably from about 1/2 to about 1; and "c" i8 the number of equivalents of halogen and can vary from a minimum of about 1/2 to a maximum of about 2, preferably from about 3 / 4 to about 1/4. The ~um of a, b, and c mu~t equAI 3Ø
For bulk polymerization, the organoammonium molybdate or tungstate or a mixture thereof, is generally employed at a level of about 0.01 to S0 milimoles molybdenum or tungsten per mole of total cycloole~n monomer, preferably 0.1 to lO millimoles. The molar ratio of alkylaluminum halide to the organoammonium molydate and/or tungstate is not critical and can be in the range of about 200 :1 and above to about 1:10 and i8 preferably from 10:1 to 2:1 of aluminum to molydenum or tungsten.
Conventional additives may also be introduced to the crude grade of cycloolefln monomers without inhibiting the objectives of the present invention in providing high quality cyclooleiin monomer~ for bulk polymerization. These conventlonal additives -12- 132~i312 include antioxidants such as Ethyl 330, a hindered phenol antioxidant; impsct modiflsrs such as the Kraton series provided by Shell Oil Company, which are generally styrene-butadiene-styrene block copolymers; ilame retardants such as antimony oxide and organohalides ( decabromodiphenylether);
filler~ such as glass or carbon fibers; pigments such a8 titanium dioxide; etc. The amount of each additive present in said volume is preferably that which provides the desired additive effect to the finished polymerized polymer.
Upon obtainlng a crude mixture of one or more cycloolefln monomers with olefinic impuritieq, th~s crude mixture of cycloolefin monomers is heated to a temperature sufficiently high to dissoctste a portion of these monomers and react the cyclopentadiene product to reduce or render inert the polymerization retarders therein, such as linear olefinic impurities. The dissocistion of the dicyclopentadiene monomer yields cyclopentadiene units which will react with linear olefinic impurities. The cyclopentsdiene will also react with other components of the crude mixture of cycloolefin monomers, including the norbornene structures of the remaining cycloolefin monomers, thus increasing their molecular weight. This may also include monocyclic olefins or the conventional additives, i . e .
flame retardanta, impact modifiers, etc. added to the crude mixture of cycloolefin monomers.
Temperatures in the range of 60 to 250C are preferred for use with a crude mixture of dicyclopentadiene monomers.
Most preferably, the temperature i~ maintained within the range of about 100C to 175C for dicyclopentsdiene monomers of about 96-98% purity.
The volume of cycloolefin monomers is maintained at an elevated temperature for at least about 0 . 25 hours and preferably from about 1 to 6 hours, most preferably about 5 hours, within a pressure vessel. The extent of dissociation and reaction varies with the time and temperature utilized. The higher temperatures provide rapid dissociation, permitting shorter hesting periods.
Trade Mark ~, .
.~ -.

-13- 132~i3~2 The extent of dissociation can be controlled by the temperature utilized or the duration of expo8ure to high temperatures. In the extreme case, a8 much a8 95% of the orig~n~ cycloolefin monomer can be dissociated and the resulting products reacted with impurities and other cycloolefin monomers to form new species, generally of higher molecular weight.
Dissociating and reacting about 5 to 50% by weight of the original cycloolefin monomer can be accomplished quite easily within a relatively short period of time at temperature values within the preferred range.
Where dicyclopentadiene is ufflized a~ the only cycloolefin monomer, the cycloolefin products of a higher molecular weight predominantly include, in decreasing concentration, tricyclo-pentadiene, tetracyclopentadiene, pentacyclopentadiene, etc.
Where dicyclopentadiene is the starting material and the heating period is less than 12 hours, resinous cycloolefin monomers with a degree of polymerization beyond pentacyclopentadiene are expected, but difffcult to detect due to low concentrations.
Ethylidenenorbornene is an example of a comonomer for use in bulk polymerizstion reactions with dicyclopentadiene. Where it is added to the crude mL~cture of dicyclopentadiene, it will react with dissociated products to yield higher molecular weight cycloolefln monomers. Typical products from ethylidene norbornene include ethylidenetetracyclododecene, ethylitenehexacycloheptadecene, etc. Homologs of ethylidenenorbornene beyond ethylidenehexacycloheptadecene are difficult to detect because small quantities are present where the heating period îs le~s than 12 hours. Vinylnorbornene, methylnorbornene are other common comonomers, and behave similarly.
A common alpha-olefin which may be added to the crude mixture of cycloolefin monomers ~s styrene, which will produce phenylnorbornene, phenyltetracyclododecene, phenylhexacyclo- - .
heptadecene, etc. if reacted with cyclopentadiene during heat-soaking of dicyclopentadiene. ~;

., : . :, , -14- 132~3t2 Polymerization grade mixtures of cycloolefin monomers are obtained from the process of the present invention. Such trested compositions provide a high degree of conversion when used as feedstocks in bulk polymerization reactions. Typical bulk polymerizations include reaction injection molding (RIM), reagent transfer molding (RTM) and liquid injection molding (LII~J) techniques.
Also provided by this invention are methods for producing polymers obtained from ring-opening, bulk polymerization.
These methods incorporate the heat treatment process of the present invention described above, wherein crude mixtures are heated to consume polymerization retsrders. It i8 important that heating take place in the absence of the complete polymerization catalyst to prevent early polymer formation.
Subsequent to enhancing the polymerization activity of the crude mixture of cycloolefin monomers, a reactive liquid mixture is formed with the treated cyclooleffn monomers. This reactive liquid mixture comprises a bulk polymerization catalyst/co-catalyst system and the treated cycloolefin monomers.
This step can be performed simply by adding the complete catalyst ~ystem to the treated cyclooleffn monomers or by adding any missing components i . e. either the catalyst or co-catalyst component, depending on which component was present in the crude mixture of cycloolefin monomers during heat-soaXing.
Sultable catalysts are the ammonium molybdates and tungstates previously de~cribed and suitable co-catalysts are the alkylaluminum halides described as suitable for bulk polymerization. When forming the reactive liquid mixture, the treated cyclooleffns may be used as is or may be cooled or heated prior to forming the reactive liquid mixture.
Upon formation, the reactive liquid mixture is conlreyed to a mold maintained at a temperature sufficiently high to initiate/accelerate ring-opening polymerization. Suitable mold temperatures fQll in the range of 25C to 150C. -By utilizing the bulk polymerization process of this invention, crude mixtures of one or more cycloolefin monomers . .

',' . '""', " .'' ,'' ' ;`'' :. '.' ''''"' ~.: ':' ', '''' ' ';".` ',''' '" -."';

-15- 132~3~ 2 ::

can be used as starting material8. Using this in~ention, good monomer conversion can be obtained with a crude grade starting material. The polymer~ obtained therefrom are unique in that the less reactive linear olefins in this crude mixture are incorporated into the polymer chain and are not diluen~s or plasticizers. Suitable results are obtained utilizing crude mixtures of from 97% to 989~ purity. Naturally, higher grades of purity are preferred and the process of this invention will provide beneficial results for crude mixtures of high monomer concentration, i. e. 98% to 99% but with significant amounts of polymerization retarder.
In peri'orming ~ome embodiments of the polymerization processes of the present invention, high molecular weight cycloolefin monomers are generated during heat-soaking, which are then polymerized. These processes incorporate heating conditions (duration, temperature, etc.) which render the crude mixtures of cycloolefln monomers an active polymerization grade feedstock and additionally provide cycloolefin monomers with increased molecular weight. For significant results, it is preferable that about 5% by weight of the cycloolefin monomers react with the cyclopentadiene product to provide high molecular weight species, Upon heating the crude mixture to obtain the desired polymerization activity or quality with an accompanying increase in monomer molecular weight, a reactive liquid mixture is formed as described above. This reactive liquid mixture comprises a bulk polymerization catalyst and the treated cycloolefln monomers with increased molecular weight. Upon formation, the reactive liquid mixture is conveyed to a mold maintained at a temperature sufflciently high to initiate ring-opening polymerization as described above.
Polymerization modiIiers to control pot life may be used in the bulk polymerization reactions. Exampies of such modiflers include water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, phenol, Inethyl mercaptan, 2-chloroethanol, 1, 3-Mchloro-propsnol, p-bromophenol, epichlorohydrine, ethylene oxide cyclopentene-2-hydroperoxide, cumylhydroperoxide, tertiarybutyl ;. . - ~.. i . i , .. ", , , . . .,. " . " .. ... .... . . . .. . .. ...

-16- 132~312 peroxide, ben~oyl peroxide, and air or oxygen. These are generally mixed with the alkylaluminum chloride component.
Catalyst activators, which provide a source of halogen sl~ch as SiC14, may al~o be used to improve monomer conversion.
The polymer and copolymer products produced by the polymerization procecses of this invention can include impact modifiers, antioxidants, flame retardants, pigments and the like.
These products are generally in finsl form and any additive3 thereto must be introduced prior to polymerization.
The following examples are provided to better illustrate the invention. It should be recognized that this invention includes other embodiments which are not shown with the particularity oi those below.

Experimental General Procedure for Preparation of Bulk Polymerized~olymers by a Simulated R ~tI~ I~ tbn Moldin~rocess Two formulations of cycloolefin monomer are made, A and B.
Formulation A is made by dissolving a trialkylammonium molybdate catalyst to a concentration of 0.1 normal in the cycloolefin monomer, preferably dioyclopentadiene. Formulation B is made by dissol~ring n-propanol catalyst modifier to 1 molar concentrstion, diethylaluminum chloride cocatalyst to 0 . 5 molar concentration and silicon tetrachlofide catalyst activator to 0 . ~5 molar concentration all within a second portion of cycloolefin monomer, preferably dicyclopentadiene. Samples of Formulation A and B are transferred to clean, dry bottles at room temperature and put under a nitrogen blanket. A poufing ~pout with a nitrogen inlet is put onto the formulation B bottle and the liquid contents injected into the formulation A bottle with shaking. The AIB bottle i8 fltted with a pouring spout and the contents transferred or injected into a cavity mold of about 1/8"
x 8" x 8" held at about 70C. A thermocouple inserted into the 13253~2 mold sllows for monitoring of the temperature. Time to the reaction exotherm vnlqes depending on numerous factors such a~
the mold temperature, amount of catalyst modifier and silicon tetrachloriide catalyst activator, catalyst concentration. After the exotherm, usually about 1. 5 to 3 . O minutes, the temperature drops down to the mold temperature (about 15ûC) and the mold i8 opened Qnd the plaque removed.
Percent conversion i8 an importsnt measurement and i9 done by thermalgravimetric analysis on the DuPonto 1090 thermal analyzer using the weight lo~s on heating up to 400C as an indication of unreacted monomer. If a name retardant is in the formulation, the weight lc88 just prior to the name retardant decomposition is reported.

Small Scale Bulk Polymerization Process To speed up the process of prepsring samples in the l~boratory, the same results may be obtained as those from the procedure described under the heading "Experimental" by adding -all the following ingredients sequentjially: cycloolefin monomer or monomer~i, n-propanol catalyst modifier, cocatalyst, silicon tetrachloride catalyst activator and the trialkylammonium molybdate catalyst being added last. All these ingredients are added as part of a dicyclopentadiene solution.

Examples The following examples demonstrate the enhancement of polymerization activity. Examples 1-3 and 7, 8 and 9, 10 show the polymerization of dicyclopentadiene treated by the process of this invention under different polymerqization conditions.
Contrds of high purity (9996~ dicyclopentadiene and a control of 979~ dicyclopentadiene are provided to compare polymerization results of untreated samples. Examples 9, 10 show the use of feed~tocks which contain elastomers.
-", ' . t: " ~ J

-18- 1 32~3~2 Examples 1-3 and Control (Example 43 About 50 gal. of commercial crude grade 97%
dicyclopentadiene obtained from Exxon, Inc. were heated to a temperature of about 150C for about 5 hours within a 50 gal.
Yessel under a N2 blanket.
After cooling, 83 gms of dicyclopentadiene were prepared for bulk polymerization by the procedure described under the heading "Small Scale Bulk Polymerization Procedure" for each example. Three polymerizations were performed (Examples 1-3), with different n-propanol concentrations of 1. 4, 1, 8 and 2 . 2 millimols, respectively. These polymerizations were identifled as 94-6-1, 94-6-2 and 94-6-3. It was discoYered the reaction was too fact at the lower molar concentrhtions of n-propanol for manual transfer. Special equipment can be used to enhance the rate at which the materials are transferred. Polymer products of ~ -Examples 1 and 2 were not analyzed since proper transfer to the mold could not be accomplished.
In each of the examples, the quantity of diethylaluminum chloride co-catalyst was 2 millimoles, the quantity of s~licon tetrachloride was 1 mol and the quantity of tridodecylammonium molybdate catalyst was 0 . 5 millimoles . All were introduced as a dicyclopentadiene solution. For Example 3, the reaction mixture was tran~erred to a mold maintained at sbout 70C. The reactive sample achieved a maximum mold temperature of about 184 after 1 min. After cooling, the molded part wa~ released and analyzed for percent conversion by thermal gravimetric analysis as described above under the heading "Experimental".
The crude grade dicyclopentadiene, treated by the process of thi~ invention, was found to attain about 97 . 696 conversion to polymer.
As a control (Example 4), another sample (about 83 gms) of commercial crude grade 97% dicyclopentadiene obtained from Exxon, Inc. was polymerized, without treatment by the process o~ this invention. This control, or Example 4, was identified as run 94-7. The same condition~ as ~xample 1 were used except -19- 132~3~2 ~

the reaction did not proceed a~ quickly so as to prevent transfer to the mold. The quantitiei~ of catalyst, co-catalysts, alcohol modifier snd silicon tetrachloride were as reported for Example 1. The mold temperature was mnintained at 70C and the thermocouple was found to read a maximum temperature of 120C
after 1 1/2 min. After the polymerized product was cooled and released from the mold, it was analyzed by a thermal gravimetfic analysis as described above under the heading "Experimental".
The untreated crude grade dicyclopentadiene attained about 94.6% conversion to polymer product.
. ., Conclusion The process of the present invention provided an increase in polymerization activity of the crude grade dicyclopentadiene as shown by an increase in the degree of conversion from about 94.6% to about 97.6% and a decrease in reaction time from 1 1/2 to one minute, even though more propanol modifier was used.

Comparative Examplei~ 5-6 To establish a comparison of the treated crude grade dicyclopentadiene, two samples of commercial polymerizistion grade 99% dicyclopentadiene obtained from Exxon, Inc., idenfffied as runs 48-5-1 and 48-5-2, were polymerized in accordance with the procedures described under the hesding "Small Scale Bulk Polymerization Process. n In each example, about 80 gms of 99%
dlcyclopentadiene w~re introduced into a dry bottle followed by 2 millimoles of n-propanol, 2 millimole~ of diethylaluminum chloride co-catalyst, 1 millimole of silicon tetrachloride catalyst acffvator snd 0 . 5 millimoles of tridodecylammonium molybdate as dicyclopentadiene solutions. The bottle was shaken and the content~ transferred into 8 cavity mold of about 1/8" x 8" x 8"
held at about 50C for each example. A thermocouple was mounted in the mold and the maximum temperature recorded for each example was about 162C during polymerizetion with .

-20~ ~32~3~2 reaction time to maximum temperattlre of 0 . 95 and 1 minute, respectively. After each polymerization was complete, the molded part was allowed to cool and it was then removed from the mold. Each molded part was analyzed for percent conversion as described in the disclosure under the heading "Experimental."
The percent conversion was found to be 97 . 4% and 96 . 8% for each example, re~pectively.

Example~ 7-8 About 400 gms of commercial crude grade 97%
dicyclopentadiene obtained from Exxon, Inc. were heated to a temperature of about 165C for about 5 hours within a 1000 ml vessel under a N2 blanket.
After cooling, 80 gms of the treated dicyclopentadiene were prepared for bulk polymerization for each of Examples 7 and 8 by the procedure described under the heading "Small Scale BulX
Polymerization Process. " Examples 7 and 8 polymerization runs were identii'ied as 94-5-1 and 94-5-2, reQpectively. Each polymerization run utilized different quantities of n-propanol catalyst modifier. In Example 7, 1. 8 millimoles of n-propanol were used while in Example 8, 1.4 millimoles of n-propanol s~ere used. For each of Examples 7 and 8, The quantity of diethylaluminum chloride co-cataly~t was 2 millimole~, the quantity of silicon tetrachloride activator was 1 millimole and the qusntity of tridodecyl ammonium molybdate was 0.5 millimoles.
Each o~ Examples 7 and 8 were molded in accordance with the procedures defined under the heading "Experimental. " The mold temperature for Example 7-was about 60C and the reagents achieved a maximum temperature of 155C in 3 min. For Example 8, the mold temperature was 70C and the reagents achieved a maximum temperature of 170C in 0 . 8 min . The longer reaction time in Example 7 relates to the higher alcohol level. After reaction was complete, the molded part was allowed to cool and then removed i'rom the mold. The degree of conversion was determined by thermal gravimetric analysis on a duPont 1090 . ~ -.

thermal analyzer for each of Example8 7 and 8. Weight loss at 400C wa~ tsken as an indicatioll of unreacted monomer. For Example 7, the percent conversion was 95.5%. For Example 8, the percent conversion was 97.2% .

Comparative ExamE~s To provide a general compar~son, two polymerizations were run which were identified as runs 212-1 and 212-2. In each of these runs, samples of the crude grade 97% dicyclopentadiene described in Examples 7 and 8, were polymerized without treatment. The monomers were mixed with similar quantities of catalyst, co-catalyst, and SlCl4 activator. For run 212-1, 1.5 millimoles of propanol were added. For run 212-2, 1.3 millimoles of propanol were added. The mold temperatures were maintained at 55C. (Reaction 212-1 peaked at 94C after 4 min., 212-2 at 7BC in 5 min. 15 sec.) The degree of conversion for run 212-1 was 94.1% and for run 212-2, it was 91.5%. ~
' , Conclusion , .
~;These example~ show an improvement in polymerization activity for 979~ pure dicyclopentadiene when treated by the process of this invention.

.
~ ~Examples 9 and 10 ~ -.
Two additional sample~ of the treated crude grade 97% -~
dicyclopentadiene, reported in Examples 7 and 8 were used for Examples 9~and 10.
About 81 gms dicyclopentadiene were prepared for bulk polymerization by the procedure described above under the heading "Small Scale Bulk Pol3~merizstion Procedure" for each ~ -example. These~ examples were identified as runs 98-S and 98-6.
For both Examples, the fol~owine were added to the dicyclopentadiene: 4 ml of .5 molar diethylaluminum chloride .
: . ' . ' `--` 132~3~2 co-cataly~t, 2 . 2 ml of 1. On molar n-propanol, and 5 ml of O .1 N
tridodecylammonium molybdate and 4 ml of O . i5 molar silicon tetrachloride all in dicyclopentadiene solutions. For Example 9, 1. 5 gms of elastomer Viqtanex*MML-80 were added. For Example 10, 2 . s gms of Diene 55 elastomer were added. These ingredients we~e combined, shaken and injected into a mold csvity having the dimensions 1/8" x 8" Y~ 8". The mold temperature wac maintained ae 50C for Example 9 and 60C for Example 10. The maximum temperature achieved during polymerization in Example 9 was about 132C in 2 . 6 min. while the maximum temperature in Exsmple 10 was sbout 149C in 2 . 2 min. After the reaction was complete, the molded psrt was allowed to cool and was then removed from the mold. The percent conversion was determined utilizing thermal gravimetric analysis with a DuPont 1090 thermal analyzer u8ing the weight 1088 on heating up to 400C as an indication of unreacted monomer. The percent monomer conversion for Example 9 was 96.69~ and the percent conversion for Example 10 was 97.3%.
. .
Conclusion These examples show the treatment of crude grade dicyclopentadiene by the process of this invention provides high monomer conversions even where additives, such as elastomers are present.

While the invention has been disclosed in this patent application by reference to the details of preferred embodiments of the invention, it is to be understood that this disclosure is intended in an illustrative rather than in a limiting sense, as it is contemplated that modifications will readily occur to those skilled in the art, within the spirit of the invention and the scope of the appended claims.
-~
* Trade Mark

Claims

1. A method for enhancing the polymerization activity of crude grade cycloolefin monomers comprising:
providing a crude grade monomer mixture of one or more cycloolefin monomers having at least one norbornene functional group, said crude grade mixture containing polymerization retarding impurities in amounts sufficient to reduce the degree of monomer conversion upon polymerization by at least 1%, as measured by thermal gravimetric analysis on a thermal analyzer utilizing the weight loss of a polymerized sample up to 400°C as the weight of unreacted monomer;
said crude grade monomer mixture containing at least about 10 weight percent dicyclopentadiene monomer, based on the total weight of the crude grade mixture;
heating said crude grade monomer mixture to a temperature sufficiently high and for a period sufficiently long to dissociate a portion of the dicyclopentadiene monomers to cyclopentadiene and to react said cyclopentatiene with the polymerization retarding impurities in a quantity sufficient to increase the degree of monomer conversion by at least 1% as measured by thermal gravimetric analysis on a thermal analyzer utilizing the weight loss of a polymerized sample up to 400°C as the weight of unreacted monomer;
wherein the crude grade monomer mixture is maintained free of a complete polymerization catalyst/co-catalyst system.

2. A method as in claim 1 wherein the polymerization retarding impurities in said crude grade monomer mixture comprise linear olefinic impurities.

3. A method as in claim 1 wherein the polymerization retarding impurities in said crude grate monomer mixture comprise linear olefinic impurities in an amount of from about 0.25 weight percent up to about 10 weight percent of the crude grade monomer mixture.

4. A method for enhancing the polymerization activity of crude grade cycloolefin monomers comprising:
providing a crude grade monomer mixture of one or more cycloolefin monomers having at least one norbornene functional group, said crude grade monomer mixture containing polymerization retarding impurities comprising linear olefinic impurities in an amount of from 1% to 10% by weight based on the weight of the total crude grade monomer mixture;
said crude grade monomer mixture containing at least about 25 weight percent dicyclopentadiene monomer, based on the total weight of the total crude grade monomer mixture;
heating said crude grade monomer mixture to a temperature sufficiently high and for a period sufficiently long to dissociate a portion of the dicyclopentadiene monomers to cyclopentadiene and reacting the cyclopentadiene with the linear cycloolefinic impurities in an amount sufficient to provide an increase in the degree of monomer conversion of at least 1%, as measured by thermal gravimetric analysis on a thermal analyzer utilizing the weight loss of a polymerized sample up to 400°C as the weight of unreacted monomer;
wherein the crude grade monomer mixture is maintained substantially free of a complete polymerization catalyst/co-cetalyst system.

5. A method as in claim 4 wherein the one or more cycloolefin monomers are comprised substantially of dicyclopentadiene.

6. A method as in claim 4 wherein the crude grade monomer mixture of one or more cycloolefin monomers additionally comprises one component selected from the group consisting of catalysts for ring-opening polymerization in bulk and co-catalysts for ring-opening polymerization in bulk.

7. A method as in claim 4 wherein the crude grade monomer mixture of one or more cycloolefin monomers is heated to a temperature in the range of about 60°C to about 250°C for a period of at least about 0.25 hours.

8. A method for enhancing the polymerization activity of crude grade cycloolefin monomers comprising:
providing a crude grade monomer mixture of one or more cycloolefin monomers having at least one norbornene functional group, said crude grade mixture comprising from 1 to 10% by weight linear olefinic impurities and oxygen containing impurities, said crude grade monomermixture containing at least about 25 weight percent dicyclopentadiene monomer, based on the total weight of the mixture;
heating the crude grade monomer mixture to a temperature in the range of about 100°C to about 175°C for a period of from 1 to 6 hours;
wherein the crude grade monomer mixture is maintained substantially free of a complete polymerization catalyst/co-catalyst system.

9. A composition produced by the process of claim 8.

10. A composition as in claim 9 obtained from commercial crude grade 97%-98% dicyclopentadiene which exhibits a degree of monomer conversion upon polymerization that is equal to or greater than commercial polymerization grade 99%
dicyclopentadiene.

11. A method for producing ring-opened polymerized polymers comprising:

(a) providing a crude grade monomer mixture of one or more cycloolefins having at least one norbornene functional group, said crude grade monomer mixture comprising about 1 to 10% by weight linear olefinic impurities and at least about 25% by weight dicyclopentadiene:
(b ) heating the crude grade monomer mixture to a temperature sufficiently high and for a period sufficiently long to dissociate a portion of the dicyclopentadiene monomer to cyclopentadiene and to react the cyclopentadiene with the linear olefinic impurities in an amount sufficient to increase the degree of monomer conversion by at least 1% as measured by thermal gravimetric analysis on a thermal analyzer, utilizing the weight loss of a polymerized sample up to 400°C as the weight of unreacted monomer;
wherein the crude grade monomer mixture is maintained substantially free of a complete ring-opening polymerization catalyst/co-catalyst system during step (b);
(c) forming a reactive liquid mixture comprising the heated crude grade monomer mixture of step (b) and a complete ring-opening bulk polymerization catalyst/co-catalyst system; and (d) conveying said reactive liquid mixture into a mold maintained at a temperature sufficiently high to thermally accelerate ring-opening polymerization.

12. A method as in claim 11 wherein the crude grade monomer mixture is heated to a temperature in the range of about 60°C to about 250°C for a period of at least about 0.25 hours in step (b) and the crude grade monomer mixture comprises commercial crude grade 97%-98% dicyclopentadiene.

13. A method for producing high molecular weight ring-opening polymerized polymers comprising:
(a) providing a commercial crude grade 97%-98%
dicyclopentadiene monomer which comprises polymerization retarding impurities in an amount sufficient to provide a degree of conversion below 95% as measured by thermal gravimetric analysis on a DuPont 1090 thermal analyzer utilizing the weight loss of a polymerized sample up to 400°C as the weight of unreacted monomer.
(b) heating the crude grade dicyclopentadiene to a temperature in the range of about 140°C to about 175°C for a period of about 1 to 6 hours to dissociate a portion of the dicyclopentadiene monomers to cyclopentadiene and react the cyclopentadiene with both dicyclopentadiene and the polymerization retarding impurities in an amount sufficient to increase the degree of monomer conversion by at least 1%
as measured by thermal gravimetric analysis on a DuPont 1090 thermal analyzer utilizing the weight loss of a polymerized sample up to 400°C as the weight of unreacted monomer;
wherein the crude grade dicyclopentadiene is maintained substantially free of a complete bulk polymerization catalyst/co-catalyst system during step (b);
(c) forming a reactive liquid mixture comprising the heated crude grade dicyclopentadiene and a complete ring-opening, bulk polymerization catalyst/co-catalyst system and (d) injecting said reactive liquid mixture into a mold maintained at a temperature sufficiently high to thermally accelerate ring-opening polymerization.

14. A method as in claim 13 wherein heating the commercial crude grade 97%-98% dicyclopentadiene provides a cycloolefin monomer mixture having a degree of monomer conversion of greater than about 97%.

15. A composition comprising a polymer produced in accordance with the method of claim 13.

16. A composition as in claim 15 additionally comprising additives selected from the group consisting of flame retardants, anti-oxidants, impact modifiers and pigments.